JP5951402B2 - Non-aqueous electrolyte secondary battery and manufacturing method thereof - Google Patents

Description

  The present invention relates to a non-aqueous electrolyte secondary battery.

  In recent years, attempts have been made to use nonaqueous electrolyte secondary batteries in, for example, electric vehicles and hybrid cars. In such applications, in addition to high output, a long life is strongly required.

  For example, Patent Document 1 describes that the cycle life of a nonaqueous electrolyte secondary battery can be improved by adding lithium bis (oxalate) borate (LiBOB) to the nonaqueous electrolyte of the nonaqueous electrolyte secondary battery. .

JP 2009-245828 A

  As a result of intensive studies, the inventors have found that when LiBOB is added to the non-aqueous electrolyte of the non-aqueous electrolyte secondary battery, the cycle life is improved, but in the event of abnormalities such as battery collapse due to external impact, Has found that it tends to generate heat. As a result, the present invention has been achieved.

  A main object of the present invention is to provide a non-aqueous electrolyte secondary battery in which heat generation inside the battery is suppressed even in the case of an abnormality as described above.

The nonaqueous electrolyte secondary battery according to the present invention includes an electrode body, a nonaqueous electrolyte, a container, and a wiring material. The electrode body has a positive electrode, a negative electrode, and a separator. The negative electrode is opposed to the positive electrode. The separator is disposed between the positive electrode and the negative electrode. The non-aqueous electrolyte includes lithium bis (oxalate) borate (LiBOB). The container contains an electrode body and a nonaqueous electrolyte. The container is provided with a terminal. The wiring material connects the terminal and the electrode body. The cross-sectional area of the wiring material is 1.5 mm ² or more.

  According to the present invention, it is possible to provide a non-aqueous electrolyte secondary battery in which the inside of a battery is unlikely to generate heat even when there is an abnormality such as battery collapse due to external impact.

1 is a schematic perspective view of a nonaqueous electrolyte secondary battery according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view taken along line II-II in FIG. 1. FIG. 3 is a schematic cross-sectional view taken along line III-III in FIG. 1. FIG. 4 is a schematic cross-sectional view taken along line IV-IV in FIG. 1. It is a schematic sectional drawing of a part of electrode body in one embodiment of the present invention. It is a schematic perspective view of the wiring material in one embodiment of the present invention.

  Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiment is merely an example. The present invention is not limited to the following embodiments.

  Moreover, in each drawing referred in embodiment etc., the member which has a substantially the same function shall be referred with the same code | symbol. The drawings referred to in the embodiments and the like are schematically described. A ratio of dimensions of an object drawn in a drawing may be different from a ratio of dimensions of an actual object. The dimensional ratio of the object may be different between the drawings. The specific dimensional ratio of the object should be determined in consideration of the following description.

  A nonaqueous electrolyte secondary battery 1 shown in FIG. 1 is a rectangular nonaqueous electrolyte secondary battery. The nonaqueous electrolyte secondary battery 1 can be used for any application, but is preferably used for, for example, an electric vehicle and a hybrid vehicle. The capacity of the nonaqueous electrolyte secondary battery 1 is usually 5 Ah to 50 Ah.

  The nonaqueous electrolyte secondary battery 1 has a container 10 shown in FIGS. 1 to 4 and an electrode body 20 shown in FIGS.

  As shown in FIG. 5, the electrode body 20 includes a positive electrode 21, a negative electrode 22, and a separator 23. The positive electrode 21 and the negative electrode 22 are opposed to each other. A separator 23 is disposed between the positive electrode 21 and the negative electrode 22. The positive electrode 21, the negative electrode 22, and the separator 23 are rolled and then pressed into a flat shape. That is, the electrode body 20 is constituted by a flat wound body of the positive electrode 21, the negative electrode 22 and the separator 23.

The positive electrode 21 includes a positive electrode current collector 21a and a positive electrode active material layer 21b. The positive electrode current collector 21a can be made of, for example, aluminum or an aluminum alloy. The thickness of the positive electrode current collector 21a is, for example, preferably about 0.5 mm to 1.5 mm, and more preferably about 0.6 mm to 1.0 mm. The positive electrode active material layer 21b is provided on at least one surface of the positive electrode current collector 21a. The positive electrode active material layer 21b contains a positive electrode active material. Examples of the positive electrode active material preferably used include lithium oxide containing at least one of cobalt, nickel and manganese. Cobalt, specific examples of the lithium oxide containing at least one of nickel and manganese, for example, lithium-containing nickel-cobalt-manganese composite oxide _{(LiNi x Co y Mn z O} 2, x + y + z = 1,0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1), lithium cobaltate (LiCoO ₂ ), lithium manganate (LiMn ₂ O ₄ ), lithium nickelate (LiNiO ₂ ), or oxides thereof Examples thereof include lithium-containing transition metal composite oxides such as compounds in which a part of the transition metal contained is substituted with another element. Among them, lithium-containing nickel cobalt manganese composite oxide (LiNi _x Co _y Mn _z O ₂ , x + y + z = 1, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1), or these A lithium-containing transition metal composite oxide such as a compound in which a part of the transition metal contained in the oxide is substituted with another element is more preferably used as the positive electrode active material. The positive electrode active material layer 21b may appropriately include other components such as a conductive material and a binder in addition to the positive electrode active material.

  The negative electrode 22 includes a negative electrode current collector 22a and a negative electrode active material layer 22b. The negative electrode current collector 22a can be made of, for example, copper or a copper alloy. The thickness of the negative electrode current collector 22a is preferably, for example, about 0.5 mm to 1.5 mm, and more preferably about 0.6 mm to 1.0 mm. The negative electrode active material layer 22b is provided on at least one surface of the negative electrode current collector 22a. The negative electrode current collector 22a includes a negative electrode active material. The negative electrode active material is not particularly limited as long as it can reversibly store and release lithium. Examples of the negative electrode active material preferably used include a carbon material, a material alloyed with lithium, and a metal oxide such as tin oxide. Specific examples of the carbon material include natural graphite, artificial graphite, mesophase pitch-based carbon fiber (MCF), mesocarbon microbeads (MCMB), coke, hard carbon, fullerene, and carbon nanotube. Examples of the material to be alloyed with lithium include one or more metals selected from the group consisting of silicon, germanium, tin, and aluminum, or one or more types selected from the group consisting of silicon, germanium, tin, and aluminum. The thing consisting of the alloy containing a metal is mentioned. Of these, natural graphite, artificial graphite, and mesophase pitch carbon fiber (MCF) are preferably used as the negative electrode active material. The negative electrode active material layer 22b may appropriately include other components such as a conductive material and a binder in addition to the negative electrode active material.

  The separator can be constituted by, for example, a porous sheet made of a resin such as polyethylene or polypropylene.

  The electrode body 20 is accommodated in the container 10. A non-aqueous electrolyte is also stored in the container 10. The non-aqueous electrolyte contains lithium bis (oxalate) borate (LiBOB) as a solute. The content of LiBOB in the non-aqueous electrolyte is preferably 0.05 mol / L to 0.20 mol / L, and more preferably 0.10 mol / L to 0.18 mol / L. In addition, the range of preferable content of LiBOB is based on the non-aqueous electrolyte in the non-aqueous electrolyte secondary battery after assembly and before the first charge. The reason for setting such a standard is that when a non-aqueous electrolyte secondary battery containing LiBOB is charged, its content gradually decreases.

In addition to LiBOB, the nonaqueous electrolyte is, for example, LiXF _y (wherein X is P, As, Sb, B, Bi, Al, Ga or In, and X is P, As or Sb) y is 6, X is B, Bi, the y when Al, Ga or in, a 4), lithium perfluoroalkyl sulfonic acid imide _{LiN (C m F 2m + 1} SO 2) (C n F 2n + 1 SO 2) (wherein, m and n are each independently an integer of 1 to 4), lithium perfluoroalkyl sulfonic acid methide _{LiC (C p F 2p + 1} SO 2) (C q F 2q + 1 SO 2) (C r F 2r + 1 SO ₂ ) (wherein p, q and r are each independently an integer of 1 to 4), LiCF ₃ SO ₃ , LiClO _4, Li ₂ B ₁₀ Cl ₁₀ and Li ₂ B ₁₂ Cl ₁₂ etc. are mentioned. Among these, as solutes, LiPF ₆ , LiBF ₄ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ), It may contain at least one of LiC (CF ₃ SO ₂ ) ₃ , LiC (C ₂ F ₅ SO ₂ ) ₃ and the like. The nonaqueous electrolyte may contain, for example, a cyclic carbonate, a chain carbonate, or a mixed solvent of a cyclic carbonate and a chain carbonate as a solvent. Specific examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, and the like. Specific examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and the like.

  The container 10 includes a container body 11 and a sealing plate 12. The container body 11 is provided in a rectangular tubular shape whose one end is closed. The container body 11 has an opening. This opening is closed by the sealing plate 12. Thereby, a rectangular parallelepiped internal space is defined. The electrode body 20 and the nonaqueous electrolyte are accommodated in this internal space.

  A positive electrode terminal 13 and a negative electrode terminal 14 are attached to the sealing plate 12. Each of the positive terminal 13 and the negative terminal 14 and the sealing plate 12 are electrically insulated by an insulating material (not shown).

  As shown in FIGS. 2 and 4, the positive electrode terminal 13 is electrically connected to the positive electrode current collector 21 a of the positive electrode 21 by the positive electrode wiring member 15. The positive electrode wiring member 15 can be made of, for example, aluminum or an aluminum alloy. As shown in FIGS. 2 and 3, the negative electrode terminal 14 is electrically connected to the negative electrode current collector 22 a of the negative electrode 22 by the negative electrode wiring member 16. The negative electrode wiring member 16 can be made of, for example, copper or copper alloy.

  The positive electrode wiring material 15 and the negative electrode wiring material 16 can be constituted by, for example, a wiring material 17 shown in FIG. The wiring member 17 has at least one first portion 17a and a second portion 17b. The first portion 17a is electrically connected to the positive electrode 21 or the negative electrode 22 by being joined by the positive electrode current collector 21a or the negative electrode current collector 22a by welding or the like. In the present embodiment, two first portions 17a are provided, and the electrode body 20 is sandwiched between the two first portions 17a.

  The first portion 17a is electrically connected to the second portion 17b. The second portion 17 b is arranged closer to the sealing plate 12 than the electrode body 20. The second portion 17 b is electrically connected to the positive terminal 13 or the negative terminal 14. Specifically, the second portion 17 b of the wiring member 17 constituting the positive electrode wiring member 15 is electrically connected to the positive electrode terminal 13. A second portion 17 b of the wiring member 17 constituting the negative electrode wiring member 16 is electrically connected to the negative electrode terminal 14.

  The cross-sectional area of the wiring material is appropriately set according to the capacity of the nonaqueous electrolyte secondary battery. Usually, the cross-sectional area of the wiring material is set to a value that does not cause a large power loss due to the wiring material. From this viewpoint, it is considered preferable that the cross-sectional area of the wiring material is sufficiently large. However, if the cross-sectional area of the wiring material is too large, the wiring material becomes large and heavy. Therefore, the nonaqueous electrolyte secondary battery becomes larger and heavier. Accordingly, the wiring material is designed to be as thin and small as possible within a range in which a large power loss is not caused by the wiring material.

For example, when the battery capacity is 5 to 50 Ah as in the non-aqueous electrolyte secondary battery 1 of this embodiment, the cross-sectional area of the wiring material is generally about 1.5 to 10 mm ^2. Is.

As described above, in the nonaqueous electrolyte secondary battery 1, the nonaqueous electrolyte contains LiBOB. For this reason, an improved cycle life can be realized. However, as a result of intensive studies by the present inventors, it has been found that a non-aqueous electrolyte secondary battery in which the non-aqueous electrolyte contains LiBOB tends to generate heat inside the battery when there is an abnormality such as battery collapse due to an external impact. . It is assumed that this is because the electrode body 20 is heated at the time of the abnormality as described above, and a reaction product derived from LiBOB causes a new exothermic reaction when the temperature exceeds a certain temperature. Here, in the nonaqueous electrolyte secondary battery 1, the cross-sectional area of the wiring member 17 (specifically, the portion connected to the current collectors 21 a and 22 a of the wiring member 17, and the portion connected to the terminals 13 and 14) The cross-sectional area of the thinnest part of the connection part connecting the ^two ) is 1.5 mm ² or more. For this reason, the heat of the electrode body 20 tends to diverge through the wiring member 17 and the container 10. That is, since the temperature rise of the electrode body 20 of the non-aqueous electrolyte secondary battery 1 is suppressed at the time of the abnormality as described above, an exothermic reaction caused by the temperature rise can be avoided.

From the viewpoint of making the nonaqueous electrolyte secondary battery 1 more difficult to generate heat, the cross-sectional area of the wiring member 17 is preferably 1.5 mm ² or more, and more preferably 3.0 mm ² or more. However, if the cross-sectional area of the wiring member 17 is too large, the nonaqueous electrolyte secondary battery 1 may become too large or the weight of the nonaqueous electrolyte secondary battery 1 may increase excessively. Therefore, the cross-sectional area of the wiring member 17 is preferably 10 mm ² or less, and more preferably 7 mm ² or less. Similarly, the thickness of the wiring member 17 is preferably 0.5 mm or more, and more preferably 0.6 mm or more. The thickness of the wiring member 17 is preferably 1.5 mm or less, and more preferably 1.0 mm or less.

  Further, from the viewpoint of making the nonaqueous electrolyte secondary battery 1 more difficult to generate heat, the thermal conductivity of the wiring member 17 is preferably 150 W / m · K or more, and preferably 200 W / m · K or more. preferable.

  In addition, according to the said structure, when a nonaqueous electrolyte secondary battery is exposed to a low temperature environment, since the temperature inside a battery will also fall easily, output characteristics will fall. In order to suppress a decrease in output characteristics even in a low temperature environment, the nonaqueous electrolyte preferably contains lithium difluorophosphate. The content of lithium difluorophosphate in the non-aqueous electrolyte is preferably 0.01 mol / L to 0.20 mol / L, and more preferably 0.03 mol / L to 0.10 mol / L. A preferable range of the content of lithium difluorophosphate is based on the nonaqueous electrolyte in the nonaqueous electrolyte secondary battery after assembly and before the first charge. The reason for setting such a standard is that when a non-aqueous electrolyte secondary battery containing lithium difluorophosphate is charged, its content gradually decreases.

  LiBOB only needs to be present in the electrolyte immediately after the non-aqueous electrolyte secondary battery is assembled. For example, after charging / discharging after assembly, LiBOB may exist as a modified LiBOB. In some cases, at least a part of LiBOB or a modified LiBOB exists on the negative electrode active material layer. Such a case is also included in the technical scope of the present invention.

DESCRIPTION OF SYMBOLS 1 ... Nonaqueous electrolyte secondary battery 10 ... Container 11 ... Container main body 12 ... Sealing board 13 ... Positive electrode terminal 14 ... Negative electrode terminal 15 ... Positive electrode wiring material 16 ... Negative electrode wiring material 17 ... Wiring material 17a ... 1st part 17b ... 1st part 2 part 20 ... electrode body 21 ... positive electrode 21a ... positive electrode current collector 21b ... positive electrode active material layer 22 ... negative electrode 22a ... negative electrode current collector 22b ... negative electrode active material layer 23 ... separator

Claims (4)

A positive electrode, wherein the negative electrode is the positive electrode and the counter, the positive electrode and have a a separator disposed between the negative electrode, the positive electrode and the negative electrode with flat wound body in which the separator is wound An electrode body,
A non-aqueous electrolyte comprising lithium bis (oxalate) borate (LiBOB);
A rectangular container body having an opening, a positive electrode terminal and a sealing plate to which the negative electrode terminal is attached and sealing the opening, and a container for storing the electrode body and the nonaqueous electrolyte;
A wiring material connecting the positive electrode terminal or the negative electrode terminal and the electrode body;
With
Cross-sectional area of the wiring member ^is a 3.0 mm 2 to 10 mm ^2,
The wiring material has a thermal conductivity of 150 W / m · K or more,
The wiring material has a thickness of 0.5 mm or more,
The capacity is 5-40Ah,
The non-aqueous electrolyte comprises lithium difluorophosphate;
The positive electrode includes a positive electrode current collector, the both sides are not the positive electrode active material layer is formed portion of the positive electrode current collector on the end of the positive electrode is formed on both surfaces of the positive electrode current collector to be provided wherein the positive electrode active material layer,
The negative electrode was formed on both sides of the negative electrode current collector so that a negative electrode current collector and a portion where the negative electrode active material layer was not formed on both sides of the negative electrode current collector were provided at the end of the negative electrode wherein said negative electrode active material layer,
In the positive electrode current collector provided at the end of the positive electrode, portions where the positive electrode active material layer is not formed on both surfaces of the positive electrode current collector extend the winding axis of the electrode body that is the wound body. while being arranged on one end side in the direction, it is arranged on the side wall portion that is disposed on one end side in the longitudinal direction of and vertically arranged the sealing plate against the sealing plate in the container body ,
In the negative electrode current collector provided at the end of the negative electrode, the portion where the negative electrode active material layer is not formed on both surfaces of the negative electrode current collector extends the winding axis of the electrode body that is the wound body while being disposed on the other end side in the direction, it is arranged on the side wall portion arranged on the other end side in the longitudinal direction of and vertically arranged the sealing plate against the sealing plate in the container body ,
The wiring member is connected to a portion where the positive electrode active material layer is not formed in the positive electrode current collector, or a portion where the negative electrode active material layer is not formed in the negative electrode current collector,
The said wiring material is a nonaqueous electrolyte secondary battery connected to the said positive electrode terminal or the said negative electrode terminal between the said electrode body and the said sealing board. A positive electrode, wherein the negative electrode is the positive electrode and the counter, the positive electrode and have a a separator disposed between the negative electrode, the positive electrode and the negative electrode with flat wound body in which the separator is wound An electrode body,
A non-aqueous electrolyte,
A rectangular container body having an opening, a positive electrode terminal and a sealing plate to which the negative electrode terminal is attached and sealing the opening, and a container for storing the electrode body and the nonaqueous electrolyte;
A wiring material connecting the positive electrode terminal or the negative electrode terminal and the electrode body;
With
Cross-sectional area of the wiring member ^is a 3.0 mm 2 to 10 mm ^2,
The wiring material has a thermal conductivity of 150 W / m · K or more,
The wiring material has a thickness of 0.5 mm or more,
The capacity is 5-40Ah,
The positive electrode includes a positive electrode current collector, the both sides are not the positive electrode active material layer is formed portion of the positive electrode current collector on the end of the positive electrode is formed on both surfaces of the positive electrode current collector to be provided wherein the positive electrode active material layer,
The negative electrode was formed on both sides of the negative electrode current collector so that a negative electrode current collector and a portion where the negative electrode active material layer was not formed on both sides of the negative electrode current collector were provided at the end of the negative electrode wherein said negative electrode active material layer,
In the positive electrode current collector provided at the end of the positive electrode, portions where the positive electrode active material layer is not formed on both surfaces of the positive electrode current collector extend the winding axis of the electrode body that is the wound body. while being arranged on one end side in the direction, it is arranged on the side wall portion that is disposed on one end side in the longitudinal direction of and vertically arranged the sealing plate against the sealing plate in the container body ,
In the negative electrode current collector provided at the end of the negative electrode, the portion where the negative electrode active material layer is not formed on both surfaces of the negative electrode current collector extends the winding axis of the electrode body that is the wound body while being disposed on the other end side in the direction, it is arranged on the side wall portion arranged on the other end side in the longitudinal direction of and vertically arranged the sealing plate against the sealing plate in the container body ,
The wiring member is connected to a portion where the positive electrode active material layer is not formed in the positive electrode current collector, or a portion where the negative electrode active material layer is not formed in the negative electrode current collector,
The wiring material is a method for producing a non-aqueous electrolyte secondary battery connected to the positive terminal or the negative terminal between the electrode body and the sealing plate,
A method for producing a nonaqueous electrolyte secondary battery, comprising the step of housing the nonaqueous electrolyte containing lithium bis (oxalate) borate (LiBOB) and lithium difluorophosphate in the container. The content of lithium bis (oxalate) borate (LiBOB) in the non-aqueous electrolyte is 0.05 mol / L to 0.20 mol / L in the step of housing the non-aqueous electrolyte in the container. The manufacturing method of the nonaqueous electrolyte secondary battery as described.   4. The non-aqueous electrolyte according to claim 2, wherein in the step of storing the non-aqueous electrolyte in the container, the content of lithium difluorophosphate in the non-aqueous electrolyte is 0.01 mol / L to 0.20 mol / L. 5. A method for producing a water electrolyte secondary battery.

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